US4298670A - Photosensitive element for electrophotography - Google Patents

Photosensitive element for electrophotography Download PDF

Info

Publication number
US4298670A
US4298670A US06/029,111 US2911179A US4298670A US 4298670 A US4298670 A US 4298670A US 2911179 A US2911179 A US 2911179A US 4298670 A US4298670 A US 4298670A
Authority
US
United States
Prior art keywords
photoconductive
photoconductive element
resin
cds
particulate material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/029,111
Other languages
English (en)
Inventor
Keiichi Murai
Takehiko Matsuo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Application granted granted Critical
Publication of US4298670A publication Critical patent/US4298670A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material

Definitions

  • photoconductive materials such as Cu 2 O, CuI, ZnO, ZnS, ZnSe, CdS, Se-Te, CdSe, CdTe, FbS, Sb 2 S 3 , In 2 Te 3 , GeS, GeSe, Tl 2 S and the like are dispersed in thermosetting resins such as epoxy resin, unsaturated polyester resin and the like, or thermoplastic resins such as vinylchloride-vinylacetate copolymer, polyvinylchloride, polyvinylacetate, cellulose acetate, cellulose nitrate, polyacrylate, polyvinylalcohol, polyvinylbutyral and the like to form photoconductive layers for electrophotography.
  • thermosetting resins such as epoxy resin, unsaturated polyester resin and the like
  • thermoplastic resins such as vinylchloride-vinylacetate copolymer, polyvinylchloride, polyvinylacetate, cellulose acetate, cellulose nitrate, polyacrylate, polyvinyl
  • cadmium sulfide as a photoconductive particle, it is activated through doping by copper in the production thereof and, in this case, since the metallic salts added are present in the neighborhood of the surface of cadmium sulfide crystal or attached to the outer surface ofthe crystal, they should be removed by washing. However, such metallic salts cannot be completely removed by simple washing and a very small amount of the salt attaches to the outer surface of the cadmium sulfide crystalline particle. It is considered that the reduction of the characteristics of the photoconductive layer is caused by the interaction of the absorption of moisture by such salt's ion and the increase in electric conductivity as the result of the absorption of moisture.
  • CdS 10 g of CdS is dispersed in 100 ml of pure water treated with ion exchange resin (electric conductivity below 1.0 ⁇ /cm, 20° C.) and after the dispersion is boiled for two minutes, it is percolated to separate CdS.
  • the thus obtained liquid extract is cooled and the electric conductivity thereof is determined at the reduced temperature of 20° C., which shows electric conductivity of the order of 30 to 50 ⁇ /cm, but not below 30 ⁇ /cm at all.
  • the conventional washing method there can be obtained only CdS containing the remaining ion which shows electric conductivity of more than 30 ⁇ /cm by the above measurement.
  • the resistance and the electrostatic voltage contrast between light and dark portions of the photoconductive layer are reduced at high temperature and the photoconductive properties with respect to humidity (resistivity to humidity) are reduced.
  • the amount of remaining ion exceeds 50 ⁇ /cm by the above measurement, high electric conductivity due to the remaining ion appears, thereby reducing the contrast even though CdS is maintained at room temperature in the silica gel atmosphere for a week.
  • the electrostatic latent image is formed directly on a photoconductive layer and also where the electrostatic latent image is formed on an insulating layer provided on the photoconductive layer, thereby reducing the contrast of the latent image.
  • the photosensitive member in which an insulating layer is provided on the photoconductive layer and which is required for excellent capability to trap electric charges because the trapped electric charge in the photoconductive layer affects directly the latent images is liable to lose such capability to trap electric charges at high temperature and high humidity, which results in low contrast.
  • the feature of this invention resides in the removal of salt ions which are present in the neighborhood of the photoconductive particle or attached to the outer surface of the photoconductive particle by treating the photoconductive particles in an aqueous solution in the presence of an ion exchange resin, and this invention enables the photoconductive layer to retain its photoconductive properties even under the conditions of high temperature and high humidity.
  • This invention is directed to the removal of ionic impurities, which cause the reduction of photoconductive properties due to temperature and humidity, by washing the photoconductive particles in the presence of an ion exchange resin in an aqueous solution.
  • the ion exchange resin herein used may be either an anion exchange resin or a cation exchange resin.
  • the ion exchange resin may be used in the range of approximately 1/2 to 1/10 part by weight per 1 part by weight of photoconductive particle to control the remaining ion and the electric conductivity of the photoconductive particle, with approximately 1/5 part by weight being most preferred.
  • the aqueous solution if possible, needs to be pure water free of ion impurities.
  • the washing is effected for the period of from several minutes to several tons minutes.
  • the control of electric conductivity can be effectively achieved by selecting appropriately the period of washing and the amount of ion exchange resin. Where the amount of ion exchange resin is, as stated above, approximately 1/5 part by weight, the washing period is preferably approximately 15 minutes.
  • the photosensitive plate wherein there is employed photoconductive particle whose remaining ion concentration is reduced by washing in the presence of an ion exchange resin to give an electric conductivity value of below 10 ⁇ /cm retains, even when allowed to stand for 16 hours at 35° C., 85% R.H. (not at ambient humidity), a contrast of more than 90% as compared to when kept at silica gel dry condition, and thus it is commercially suitable.
  • the photosensitive plate using such photoconductive particle when allowed to stand for more than 16 hours at 35° C., 100% R.H., can retain a contrast of more than 95% as compared to when kept at ambient humidity and it shows very excellent properties with respect to humidity.
  • the control of electric conductivity is measured by the factors of the amount of ion exchange resin, washing period and so on and also is affected by the kind of photoconductive particle itself.
  • photoconductive particle suitable for such purpose not only CdS simple body but such particles as stated in the introductory portion of this specification can be employed and particularly CdSe, ZnS, (Cd-Zn)S, CdS-CdSe, etc., as well as CdS which inherently contains the remaining ion due to the activation process, are advantageously employed.
  • the photoconductive particles produced according to this invention are dispersed in a resin binder to form a photoconductive layer, which is further provided with an insulating layer to form a photosensitive plate.
  • the electrostatic contrast between the light and dark portions of the thus-prepared photosensitive plate is measured as follows.
  • the photosensitive plate is maintained at a temperature of 30° C. and a relative humidity of 85%.
  • Corona discharge of +6 KV is applied to the plate to provide surface potential of +2 KV thereon.
  • corona discharge of AC 6 KV is applied to the plate while at the same time the plate is exposed to light of 2.5 Lux.sec.
  • the plate (light portion) shows a surface potential of -150 V.
  • corona discharge of +6 KV is applied on the photosensitive plate to obtain surface potential of +2 KV thereon.
  • a corona discharge of AC 6 KV is applied thereto without the plate being exposed to the light.
  • the plate (dark portion) shows a surface potential of +500 V.
  • the potential difference between the dark portion and the light portion contrast is 650 V. Contrarily, when the aforementioned procedure is applied at the aforementioned temperature and humidity on the photosensitive plate using photoconductive particles produced in the conventional manner, not using ion exchange resin, the potential difference is lowered by approximately 50% of that of this invention. When the photosensitive plate of this invention is kept at normal temperature and humidity and the same procedure as stated above is applied on the photosensitive plate, the potential difference is approximately 700 V. This shows that the photoconductive particles of this invention are scarcely affected by temperature, humidity and so on. As is apparent from this fact, the photoconductive particles of this invention are scarcely affected by temperature and humidity and are capable of showing a contrast which is more excellent than that of the conventional particle. Although the same procedure is repeated thirty thousand, there can not be found any change of the contrast and any reduction of the contrast at high temperature and high humidity, which shows the photosensitive plate of this invention to be commercially suitable.
  • thermosetting and thermoplastic resins are employed as a binder for production of the photoconductive layer.
  • ordinary insulative resins such as polycarbonate, polyethylene, polypropylene, polystyrene, polyurethane, polyester and the like may be used and when applied by dip coating method, two liquid type of polyurethane, photocurable acrylic resins, photocurable polyester resins, photocurable epoxy resins are used to form a layer having an uniform thickness of 20 to 40 ⁇ .
  • the photoconductive layer may afford stable and high contrast even at high temperature and high humidity.
  • the photoconductive material may be used in combination with ion exchange to prepare a photoconductive layer, which is also in the scope of this invention.
  • cadmium sulfide powder was dispersed in 5 parts by weight of pure water, and 1/5 part by weight of Amberlite anion exchange resin IRA-410 (OH - type) was also added. After the dispersion was stirred for 15 minutes, cadmium sulfide was separated from the ion exchange resin to obtain cadmium sulfide and a filtrate having an electrical conductivity of below approximately 10 ⁇ /cm, which was dried by heating for 6 hours at 70° C. 10 parts by weight of cadmium sulfide so obtained and 5 parts by weight of vinylchloridevinylacetate copolymer (V-I manufactured by Morikawa Ink Co.
  • V-I vinylchloridevinylacetate copolymer manufactured by Morikawa Ink Co.
  • the paint was applied on an aluminum foil whose thickness was 50 ⁇ according to a roll-coating method to form a photoconductive layer whose thickness was 30 ⁇ when dried. Then the layer was dried at 80° C. for 30 minutes and Luminer of 25 ⁇ thickness (polyester film manufactured by Toray Co. Ltd.) was coated thereon using an adhesive of DB-9A04 (Diabond Co. Ltd.), and after it was dried at 80° C. for 5 minutes, it was laminated under pressure to produce a photosensitive plate for electrophotography. As in EXAMPLE 1, corona discharge of +6 KV was applied to the photosensitive plate so produced to provide +2 KV of surface potential of the photoconductive layer.
  • Coronadischarge of AC 6 KV was applied thereto while at the same time the whole surface was exposed to light of 2.5 Lux.sec.
  • the contrast of electrostatic potential between the plate which was exposed to light as mentioned above and another plate which was not exposed to light was determined to be 650 KV.
  • the photosensitive plate was placed at 35° C. and at high humidity of 85%, there could not be found any reduction of contrast, and when the latent image was developed with dry or wet developing method and transferred to paper a sharp image was obtained which was of high contrast.
  • the paint was applied onto an aluminum foil whose thickness was 50 ⁇ to form a photoconductive layer and then an insulating layer was provided on the photoconductive layer to form a photosensitive plate. As in EXAMPLES 1, 2 and 3, there could not be found any reduction of electrostatic contrast at high temperature and high humidity, and the image quality was excellent.
  • Cu-activated CdS was washed to remove remaining ion and to adjust the electric conductivity thereof to 8.5 ⁇ /cm by the afore-mentioned measurement.
  • 100 parts by weight of CdS so obtained was dispersed in 50 parts by weight of V-I clear (Trade name: manufactured by Morikawa Ink Co. Ltd.) and they were blended in a three rod roll mill to form a paint.
  • the paint was applied on an aluminum foil whose thickness was 50 ⁇ by knife-coating to prepare photoconductive layer having the thickness of 30 ⁇ , which was further provided with a polyester film whose thickness was 25 ⁇ to prepare a photosensitive plate of three layer construction.
  • the thus-obtained photosensitive plate was referred to as Sample A.
  • a CdS solution having an electric conductivity of 1.8 ⁇ /cm was prepared, and the CdS was used in producing a photosensitive plate in the same manner as described above.
  • the thus-obtained photosensitive plate was referred to as Sample B.
  • conventional CdS whose electric conductivity was measured to be approximately 43 ⁇ /cm, was employed to produce a photosensitive plate in the aforementioned manner.
  • the thus-obtained photosensitive plate was referred to as Sample C.
  • a photosensitive plate was prepared in the same manner as Sample A except that as the binder, 25 parts by weight of LR472 (Trade name: manufactured by Mitsubishi Rayon Co. Ltd.) was used per 100 parts by weight of CdS.
  • the thus-obtained photosensitive plate was referred to as Sample D.
  • Samples A and D in which the photoconductive particle having electric conductivity of below 10 ⁇ /cm was employed provided good images under all the conditions. Particularly, when Sample B whose electric conductivity was below 2 ⁇ /cm. was employed, there could be obtained an excellent image even at the condition of 35° C., 100% and 16 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Light Receiving Elements (AREA)
US06/029,111 1972-07-29 1979-04-11 Photosensitive element for electrophotography Expired - Lifetime US4298670A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP47076145A JPS5120276B2 (enrdf_load_stackoverflow) 1972-07-29 1972-07-29
JP47-76145 1972-07-29

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US05/838,376 Division US4183748A (en) 1972-07-29 1977-09-30 Method of removing surface ionic impurities on inorganic photoconductive material

Publications (1)

Publication Number Publication Date
US4298670A true US4298670A (en) 1981-11-03

Family

ID=13596819

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/029,111 Expired - Lifetime US4298670A (en) 1972-07-29 1979-04-11 Photosensitive element for electrophotography

Country Status (3)

Country Link
US (1) US4298670A (enrdf_load_stackoverflow)
JP (1) JPS5120276B2 (enrdf_load_stackoverflow)
DE (1) DE2338233C2 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4415643A (en) * 1980-09-03 1983-11-15 Canon Kabushiki Kaisha Process for preparing photoconductive cadmium sulfide
US4434219A (en) 1981-02-24 1984-02-28 Canon Kabushiki Kaisha Electrophotographic photosensitive member comprising photoconductive powder and a deionized binder resin
US20170342598A1 (en) * 2014-12-11 2017-11-30 Solvay Acetow Gmbh Polymer composition comprising basic additive, process and articles comprising said polymer composition

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5646565A (en) * 1979-09-21 1981-04-27 Canon Inc Manufacture of photoconductive particle
JPS6466658A (en) * 1987-09-07 1989-03-13 Hitachi Chemical Co Ltd Electrophotographic sensitive body
JPH04253062A (ja) * 1991-01-30 1992-09-08 Fuji Xerox Co Ltd 電子写真感光体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3238150A (en) * 1962-09-12 1966-03-01 Xerox Corp Photoconductive cadmium sulfide powder and method for the preparation thereof
US3592643A (en) * 1968-08-15 1971-07-13 Gen Electric Photoconductive cadmium sulfide composition and process of preparing
DE2055423A1 (en) * 1970-11-11 1972-05-18 Chemische Fabrik Budenheim, Rudolf A. Oetker, 6501 Budenheim Washing compositions - containing water-insoluble crosslinked cation -exchange polymers especially crosslinked polystyrene,polyacrylic acid
US3691104A (en) * 1969-05-15 1972-09-12 Canon Kk Process for preparing photoconductive powders
US4021237A (en) * 1974-11-14 1977-05-03 Canon Kabushiki Kaisha Process for producing cadmium sulfide for electrophotography

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1259070A (enrdf_load_stackoverflow) * 1969-07-09 1972-01-05
US3694201A (en) * 1971-01-06 1972-09-26 Xerox Corp Method for photoconductive powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3238150A (en) * 1962-09-12 1966-03-01 Xerox Corp Photoconductive cadmium sulfide powder and method for the preparation thereof
US3592643A (en) * 1968-08-15 1971-07-13 Gen Electric Photoconductive cadmium sulfide composition and process of preparing
US3691104A (en) * 1969-05-15 1972-09-12 Canon Kk Process for preparing photoconductive powders
DE2055423A1 (en) * 1970-11-11 1972-05-18 Chemische Fabrik Budenheim, Rudolf A. Oetker, 6501 Budenheim Washing compositions - containing water-insoluble crosslinked cation -exchange polymers especially crosslinked polystyrene,polyacrylic acid
US4021237A (en) * 1974-11-14 1977-05-03 Canon Kabushiki Kaisha Process for producing cadmium sulfide for electrophotography

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hackh's Chemical Dictionary, 4th Ed., 1972. *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4415643A (en) * 1980-09-03 1983-11-15 Canon Kabushiki Kaisha Process for preparing photoconductive cadmium sulfide
US4434219A (en) 1981-02-24 1984-02-28 Canon Kabushiki Kaisha Electrophotographic photosensitive member comprising photoconductive powder and a deionized binder resin
US20170342598A1 (en) * 2014-12-11 2017-11-30 Solvay Acetow Gmbh Polymer composition comprising basic additive, process and articles comprising said polymer composition
CN112375259A (zh) * 2014-12-11 2021-02-19 索尔维阿塞托有限公司 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品
US11352716B2 (en) * 2014-12-11 2022-06-07 Rhodia Acetow Gmbh Polymer composition comprising basic additive, process and articles comprising said polymer composition
CN115716938A (zh) * 2014-12-11 2023-02-28 索尔维阿塞托有限公司 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品
CN112375259B (zh) * 2014-12-11 2023-10-03 索尔维阿塞托有限公司 包含碱性添加剂的聚合物组合物，方法以及包含所述聚合物组合物的物品
US11920260B2 (en) 2014-12-11 2024-03-05 Rhodia Acetow Gmbh Polymer composition comprising basic additive, process and articles comprising said polymer composition

Also Published As

Publication number Publication date
DE2338233C2 (de) 1983-01-20
JPS4934289A (enrdf_load_stackoverflow) 1974-03-29
DE2338233A1 (de) 1974-02-14
JPS5120276B2 (enrdf_load_stackoverflow) 1976-06-23

Similar Documents

Publication Publication Date Title
DE1622364C3 (de) Elektrophotographisches Aufzeichnungsmaterial
US2993787A (en) Electrostatic printing
US3052539A (en) Electrostatic printing
DE2009346A1 (de) Elektrophotographisches Aufzeichnungsmaterial
DE1932457A1 (de) Induktionsabbildungsverfahren
US4183748A (en) Method of removing surface ionic impurities on inorganic photoconductive material
US4298670A (en) Photosensitive element for electrophotography
DE1797232A1 (de) Bildempfangsmaterial fuer elektrophotographische Verfahren
US4252883A (en) Process for producing electrophotographic photosensitive member
US4170476A (en) Layered photoconductive element having As and/or Te doped with Ga, In or Tl intermediate to Se and insulator
US3867145A (en) Methanol and heat treated zinc oxide
US3577272A (en) Method of making x-ray sensitive electroradiographic elements
US4043813A (en) Photoconductive particles of zinc oxide
DE1522598B2 (de) Elektrophotographisches Aufzeichnungsmaterial
US3543025A (en) Electroradiographic x-ray sensitive element containing tetragonal lead monoxide
US2979402A (en) Electrostatic printing
US4264696A (en) Electrophotographic photoreceptor
DE1797137A1 (de) Elektrophotographisches Aufzeichnungsmaterial
DE2710252C3 (de) Photoleitfähige Teilchen sowie ein elektrophotographisches Aufzeichnungsmaterial und eine Photozelle, deren Photoleiter-Bindemittel-Schicht diese Teilchen enthält
US4191568A (en) Photosensitive material for electrophotography with dye containing overlayer
DE2306983C3 (de) Verfahren zur Kontaktbelichtung einer aufgeladenen photoleitfähigen Schicht eines elektrophotographischen Aufzeichnungsmaterials
DE2019227C3 (de) Elektrophotographisches Aufzeichnungsmaterial
DE2227145A1 (de) Photoleitende Aufzeichnungsschichten für elektrophotographische Verfahren
DE2525318B2 (de) Elektroradiographisches aufzeichnungsmaterial sowie elektroradiographisches verahren
US4098609A (en) Method of making improved photoconductive particles

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE